DE2238330C3 - Benzoxanthene and benzothioxanthene dyes and processes for their preparation - Google Patents
Benzoxanthene and benzothioxanthene dyes and processes for their preparationInfo
- Publication number
- DE2238330C3 DE2238330C3 DE2238330A DE2238330A DE2238330C3 DE 2238330 C3 DE2238330 C3 DE 2238330C3 DE 2238330 A DE2238330 A DE 2238330A DE 2238330 A DE2238330 A DE 2238330A DE 2238330 C3 DE2238330 C3 DE 2238330C3
- Authority
- DE
- Germany
- Prior art keywords
- formula
- mixture
- dye
- group
- och
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000000975 dye Substances 0.000 title claims description 22
- 238000000034 method Methods 0.000 title claims description 7
- 238000002360 preparation method Methods 0.000 title claims description 4
- YEBQUUKDSJCPIX-UHFFFAOYSA-N 12h-benzo[a]thioxanthene Chemical compound C1=CC=CC2=C3CC4=CC=CC=C4SC3=CC=C21 YEBQUUKDSJCPIX-UHFFFAOYSA-N 0.000 title description 2
- VVZRKVYGKNFTRR-UHFFFAOYSA-N 12h-benzo[a]xanthene Chemical compound C1=CC=CC2=C3CC4=CC=CC=C4OC3=CC=C21 VVZRKVYGKNFTRR-UHFFFAOYSA-N 0.000 title description 2
- 239000000203 mixture Substances 0.000 claims description 15
- 150000007857 hydrazones Chemical class 0.000 claims description 13
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 229910052717 sulfur Chemical group 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000005521 carbonamide group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000002253 acid Substances 0.000 description 12
- 244000183685 Citrus aurantium Species 0.000 description 11
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 8
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 4
- -1 Halogen amines Chemical class 0.000 description 4
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 235000011056 potassium acetate Nutrition 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 229920000193 polymethacrylate Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920005553 polystyrene-acrylate Polymers 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- ZYECOAILUNWEAL-NUDFZHEQSA-N (4z)-4-[[2-methoxy-5-(phenylcarbamoyl)phenyl]hydrazinylidene]-n-(3-nitrophenyl)-3-oxonaphthalene-2-carboxamide Chemical compound COC1=CC=C(C(=O)NC=2C=CC=CC=2)C=C1N\N=C(C1=CC=CC=C1C=1)/C(=O)C=1C(=O)NC1=CC=CC([N+]([O-])=O)=C1 ZYECOAILUNWEAL-NUDFZHEQSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- CVBUKMMMRLOKQR-UHFFFAOYSA-N 1-phenylbutane-1,3-dione Chemical compound CC(=O)CC(=O)C1=CC=CC=C1 CVBUKMMMRLOKQR-UHFFFAOYSA-N 0.000 description 1
- JGKFWCXVYCDKDU-UHFFFAOYSA-N 2,4-dioxo-4-phenylbutanoic acid Chemical compound OC(=O)C(=O)CC(=O)C1=CC=CC=C1 JGKFWCXVYCDKDU-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- YHOLEWMSPAWWRU-UHFFFAOYSA-N 3-(hydrazinecarbonyl)-12H-benzo[a]thioxanthene-4-carboxylic acid Chemical compound C1C2=CC=CC=C2SC2=C1C1=CC=C(C(=O)NN)C(C(O)=O)=C1C=C2 YHOLEWMSPAWWRU-UHFFFAOYSA-N 0.000 description 1
- AHEFZSJNVBLWFC-UHFFFAOYSA-N 3-(hydrazinecarbonyl)-6-methoxy-12H-benzo[a]xanthene-4-carboxylic acid Chemical compound COC=1C=2OC=3C=CC=CC3CC2C2=C(C1)C(=C(C=C2)C(=O)NN)C(=O)O AHEFZSJNVBLWFC-UHFFFAOYSA-N 0.000 description 1
- SLWCDZBRDSTRLV-UHFFFAOYSA-N 3-oxo-4-phenylbutanoic acid Chemical compound OC(=O)CC(=O)CC1=CC=CC=C1 SLWCDZBRDSTRLV-UHFFFAOYSA-N 0.000 description 1
- MZPZMTFDSVTILM-UHFFFAOYSA-N 3-oxoicosanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(=O)CC(O)=O MZPZMTFDSVTILM-UHFFFAOYSA-N 0.000 description 1
- PURJGKXXWJKIQR-UHFFFAOYSA-N 4-[(4-hydroxynaphthalen-1-yl)diazenyl]benzenesulfonic acid Chemical compound C12=CC=CC=C2C(O)=CC=C1N=NC1=CC=C(S(O)(=O)=O)C=C1 PURJGKXXWJKIQR-UHFFFAOYSA-N 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
- DRSHXJFUUPIBHX-UHFFFAOYSA-N COc1ccc(cc1)N1N=CC2C=NC(Nc3cc(OC)c(OC)c(OCCCN4CCN(C)CC4)c3)=NC12 Chemical compound COc1ccc(cc1)N1N=CC2C=NC(Nc3cc(OC)c(OC)c(OCCCN4CCN(C)CC4)c3)=NC12 DRSHXJFUUPIBHX-UHFFFAOYSA-N 0.000 description 1
- 241000243251 Hydra Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- SMEGJBVQLJJKKX-HOTMZDKISA-N [(2R,3S,4S,5R,6R)-5-acetyloxy-3,4,6-trihydroxyoxan-2-yl]methyl acetate Chemical compound CC(=O)OC[C@@H]1[C@H]([C@@H]([C@H]([C@@H](O1)O)OC(=O)C)O)O SMEGJBVQLJJKKX-HOTMZDKISA-N 0.000 description 1
- GCPWJFKTWGFEHH-UHFFFAOYSA-N acetoacetamide Chemical compound CC(=O)CC(N)=O GCPWJFKTWGFEHH-UHFFFAOYSA-N 0.000 description 1
- DYRDKSSFIWVSNM-UHFFFAOYSA-N acetoacetanilide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1 DYRDKSSFIWVSNM-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 229940081735 acetylcellulose Drugs 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- OIQPTROHQCGFEF-UHFFFAOYSA-L chembl1371409 Chemical compound [Na+].[Na+].OC1=CC=C2C=C(S([O-])(=O)=O)C=CC2=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 OIQPTROHQCGFEF-UHFFFAOYSA-L 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- UZBQIPPOMKBLAS-UHFFFAOYSA-N diethylazanide Chemical compound CC[N-]CC UZBQIPPOMKBLAS-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- KRAHENMBSVAAHD-UHFFFAOYSA-N ethyl 3-(4-methoxyphenyl)-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)C1=CC=C(OC)C=C1 KRAHENMBSVAAHD-UHFFFAOYSA-N 0.000 description 1
- KQWWVLVLVYYYDT-UHFFFAOYSA-N ethyl 3-oxohexanoate Chemical compound CCCC(=O)CC(=O)OCC KQWWVLVLVYYYDT-UHFFFAOYSA-N 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 230000036449 good health Effects 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- QRXWMOHMRWLFEY-UHFFFAOYSA-N isoniazide Chemical compound NNC(=O)C1=CC=NC=C1 QRXWMOHMRWLFEY-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000005499 meniscus Effects 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- KHPXUQMNIQBQEV-UHFFFAOYSA-N oxaloacetic acid Chemical compound OC(=O)CC(=O)C(O)=O KHPXUQMNIQBQEV-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000001044 red dye Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 235000012751 sunset yellow FCF Nutrition 0.000 description 1
- 239000004173 sunset yellow FCF Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/14—Benzoxanthene dyes; Benzothioxanthene dyes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Luminescent Compositions (AREA)
Description
R4-R4-
r Y Y χ r YY χ
X Αχ-'-·.,X Αχ -'- ·.,
überfuhrt, wobei X, R1, R2, Ra, R4· R5 "nd Rh die obeneenannren Bedeutungen haben, und dieses Hydrazon in Gegenwart von basischen Kondensationsmitteln cyclisiert.überfuhrt, wherein X, R 1, R 2, Ra, R4 · R5 "n d Rh have the meanings obeneenann r s, and this hydrazone is cyclized in the presence of basic condensing agents.
2020th
R2-C-C-R1 R 2 -CCR 1
Λ Λ. Λ Λ.
ί Yί Y
Gegenstand der Erfindung sind neue wertvolle Farbstoffe, die aus dem Isomerengemisch der Formel IThe invention relates to new valuable dyes which are obtained from the isomer mixture of the formula I.
wobei X ein Sauerstoff- oder Schwefelatom. R1 ein VVasserstoffatom. eine Alkylgruppe mit I bis 20 C-Atomen, eine Methoxyearbonylmethyk AtIi- <txycarbonylmethylgruppc. eine niedere Alkoxvcarbonylgruppe oder eine Phenylgruppe. R2 eine Alkoxycarbonylgruppe mit 1 bis 20 C-Atomen. cine niedere Acvlgruppe. eine Ben/oylgi uppe. eine ('yanogruppe. eine Carbonamid- oder Phenylcarbonamidgruppe. R, und R4 gleichzeitig Waslerstoffatome oder niedere Alkoxygruppen oder R, eine niedere Alkoxygruppe und R4 ein Wasseritoffalom. R^ und R1, Wasserstoff- oder Halogenatome, niedere Alkyl-. Alkoxy- oder Alkoxycarbonylgruppen bedeuten, dadurch gckenn/eiehnei. daß man ein Benzoxanthen- oder Hen/nthionanthendiearbonsäurelivdra/id der I'd line Iwhere X is an oxygen or sulfur atom. R 1 is a hydrogen atom. an alkyl group with 1 to 20 carbon atoms, a Methoxyearbonylmethyk AtIi- <txycarbonylmethylgruppc. a lower alkoxy carbonyl group or a phenyl group. R 2 is an alkoxycarbonyl group with 1 to 20 carbon atoms. a lower acyl group. a Ben / oylgi group. a ('yano group. a carbonamide or phenylcarbonamide group. R, and R 4 simultaneously hydrogen atoms or lower alkoxy groups or R, a lower alkoxy group and R 4 a hydrogen atom. R ^ and R 1 , hydrogen or halogen atoms, lower alkyl. alkoxy groups or alkoxycarbonyl groups, as a result of the fact that a benzoxanthene or henionanthene diarboxylic acid derivative of the I'd line I
N- -NN- -N
IlIl
C--R1 C - R 1
Ac7 Ac 7
R,R,
undand
R1-C-- C -R1 R 1 -C-- C -R 1
' ί ή'ί ή
>= O> = O
R,-R, -
!I
/■''. An --NH, ! I
/ ■ ''. To --NH,
->=■■= ο -> = ■■ = ο
X-'X- '
R„R "
mit einer N'erbiiidung der Formel
R, COCH, R1 with an expression of the formula
R, COCH, R 1
bestehen, wobei X ein Sauerstoff- .ider Schwefelatom. R1 ein Wasserstoffatom, eine Alkylgruppe mit I bis 20 ( -Atomen, eine Melhox\carhonylmethyl-. Alhoxyearbonylmethylgruppe. eine niedere Alkoxycarbonylgruppe oder eine l'henylgruppe. R: eine Alkoxycarbon_\ !gruppe mn 1 hi·- 20 ('-Atomen, eine niedere Acyl- oder Men/ov Ilm lippe, cmc Cyanogriippe. eineexist, where X is an oxygen .ide sulfur atom. R 1 is a hydrogen atom, an alkyl group with 1 to 20 (atoms, a melhoxycarbonylmethyl. Alhoxyearbonylmethylgruppe. A lower alkoxycarbonyl group or a phenyl group. R : an alkoxycarbonyl group mn 1 hi · - 20 ('atoms, a lower acyl or meniscus ilm lip, cmc cyano rib
(■,<; ( aibonamid-oiler l'henv 11:11 -(innamidgi uppe. R, und R, i.'L'ieh/eiiiL' Wasserslolialonii· 'kIci niedere Mk-MWl-! lippen od'"i' U- eine niedere -\lkox\gr uppe und I' ; ein V\;i\sri-.|oli;it.'iii. R und R1, Wasserslol'l-oder(■, <; (aibonamid-oiler l'henv 11:11 - (innamidgi uppe. R, and R, i.'L'ieh / eiiiL 'Wasserslolialonii ·' kIci niedere Mk-MWl-! Lippen od '"i' U- a lower - \ lkox \ group and I '; a V \; i \ sri-. | Oli; it.'iii. R and R 1 , water lol'l- or
Halogenamine, niedere Alkyl-, Alkoxy- oder Alkoxycarbonylgruppen bedeuten, sowie ein Verfahren zu deren Herstellung.Halogen amines, lower alkyl, alkoxy or alkoxycarbonyl groups mean, as well as a method for their preparation.
Bevorzugt sind solche Verbindungen der obigen Formel I. wobei R, eine niedere Alkylgruppc. R, eine Alkoxycarbonylgruppe mit I bis 20 C-Atomen. Rs und R1, ein Wassersioffatom oder eine niedere AIkoxygruppe bedeulet und X. R, und R4 die obengenannte Bedeutung haben.Those compounds of the above formula I are preferred, where R, a lower alkyl group. R, an alkoxycarbonyl group with 1 to 20 carbon atoms. R s and R 1 , a hydrogen atom or a lower alkoxy group and X. R and R 4 have the meaning given above.
Die neuen Farbstoffe werden erhalten, wenn man to ein Bcnzoxanthcn- oder Benz.otliioxanlhendiciirbonsäurehydrazid der Formel IIThe new dyes are obtained when you to a benzoxanthine or benzotliioxane-dicirboxylic acid hydrazide of formula II
III)III)
mit einer Verbindung der Formel IIIwith a compound of the formula III
R1-COCH2- R2 (III)R 1 -COCH 2 - R 2 (III)
in Gegenwart von sauren Kondensationsmitteln in ein Hydrazon der Formel IVin the presence of acidic condensing agents into a hydrazone of the formula IV
O R1 OR 1
. 1 i. 1 i
..···,,' N N=-C--CH1R,.. ··· ,, 'NN = -C - CH 1 R,
3535
(IV)(IV)
überführt, wobei in den Formeln II. Ill und IV die Subslituenien R1. R2. Ri- R4- R< und R,, sowie X die vorstehend genannten Bedeutungen haben, und dieses Hydrazon in Gegenwart \on basischen Kondensalionsmitteln cyclisijrt.transferred, whereby in the formulas II. III and IV the subscripts R 1 . R 2 . Ri- R4- R <and R ,, and X have the meanings given above, and this hydrazone is cyclized in the presence of basic condensation agents.
Zur Herstellung der Farbstoffe verfährt man zweckmäßig so. daß man die Ausgangsverbindung II mit mindestens äquivalenten Mengen der methylenaktiven $5 Komponente III in Gegenwart von etwa 0.01 bis 0.1 Mol eines sauren Kondcnsationsmittels pro Mol Ausgangsverbindung bei erhöhter Temperatur umsetzt. This is the appropriate procedure for the preparation of the dyes. reacting the starting compound II with at least equivalent amounts of the active methylene $ 5 component III in the presence of about 0.01 to 0.1 mole of an acid per mole of starting compound Kondcnsationsmittels at elevated temperature.
Die Kondensation kann entweder in einem geeigncten organischen Lösungsmittel wie beispielsweise Isobutanol. Monomethylglykol. Chlorbenzol. Dichlorbenzol. Nitrobenzol. Dimethylformamid. N-Methylpyrrolidon. Essigsäure oder auch in einem Überschuß der Verbindung Hl bei einer Temperatur zwisehen etwa 100 und etwa 200 C. gegebenenfalls unter Druck, erfolgen. Die Reaktionsdauer liegt zwischen etwa 30 Minuten und 8 Stunden. In manchen Fällen ist es zweckmäßig, das Reaktionswasser und ändert leicht flüchtige Nebenprodukte durch Destillatioi oder Durchleitcn eines inerten Gasstromes aus de Reaktionsmischung zu entfernen.The condensation can either be in a suitable organic solvent such as Isobutanol. Monomethyl glycol. Chlorobenzene. Dichlorobenzene. Nitrobenzene. Dimethylformamide. N-methylpyrrolidone. Acetic acid or else in an excess of the compound Hl at a temperature zwisehen about 100 and about 200 C. if necessary under pressure. The reaction time is between about 30 minutes and 8 hours. In some cases it is useful to change the water of reaction and volatile by-products by distillation or passage of an inert gas stream from the Remove reaction mixture.
Das gebildete Hydrazon kann nach dem Abkühlei in üblicher Weise isoliert werden. Als saure Konden sationsmittcl kommen aromatische Sulfonsäuren wi< Benzol- oder Toluolsulfonsiiure. Alkansulfonsäurer Athansulfonsäure. Amidosulfonsäure. Mineralsäure!' wie Schwefel- oder Phosphorsäure oder auch gasförmiger Chlorwasserstoff in Betracht. Bei Verwendung von protischen Lösungsmitteln wie Fssig- odei Propionsäure wirken diese bereits als saure Kondensationsmiitel. The hydrazone formed can after cooling can be isolated in the usual way. Aromatic sulfonic acids are used as acidic condensation agents Benzene or toluenesulfonic acid. Alkanesulfonic acid athanesulfonic acid. Sulfamic acid. Mineral acid! ' such as sulfuric or phosphoric acid or gaseous hydrogen chloride. Using Protic solvents such as liquid or propionic acid already act as acidic condensation media.
Beispiele für Verbindungen der Formel III sind Acetessigsäurcmethyl-. -äthyl-. -butyl-, -isopropyl- -dodecyl-. -2-äthoxyälhylester. Butyrylessigsäureäthylester. ^-Diäthylacctessigsäurcä thy !ester. Slcaroylcssigsäureäthylester. Phenylacetessigsäurcii thy !ester. Benzoyl- und 4- Methoxybenzoylessigsäureäthylester. Oxalessigsäurediäthylesler. Acetylaceton. Benzoylaceton. ;■- Dimethylacetylaceton. Dibcnzoylmethan. !■-Alhoxvacetylacelon. Acetyl- und Benzoylbrenztraubensäureäthylester. Acelondiearbonsäuredimcthylester. Benzoylaeeionitril. Formylacetophenon. Acetessigsäureamid. Acelessigsliurcmelhyl- und diäthylamid. Acetessigsäiireanilid. -p-anisidid. -3-ehloranilid. -5 -chlor- 2 - toluidid. -o - loluidid. -cyclohexylamid. -octylamid. 2.4-Dichlorbenz.oylessigsäureainid.Examples of compounds of the formula III are methyl acetoacetate. -ethyl-. -butyl-, -isopropyl- -dodecyl-. -2-ethoxyethyl ester. Ethyl butyrylacetate. ^ -Diethylacctacetic acid acid ester. Ethyl acetate. Phenylacetoacetic acid methylate. Benzoyl and 4-methoxybenzoyl acetic acid ethyl ester. Oxaloacetic acid diethylers. Acetylacetone. Benzoylacetone. ; ■ - dimethylacetylacetone. Discoyl methane. ! ■ -Alhoxvacetylacelon. Ethyl acetyl and benzoylpyruvate. Dimethyl acelondiarboxylate. Benzoylaeeionitrile. Formylacetophenone. Acetoacetic acid amide. Acelessigsliurcmelhyl- and diethylamide. Acetoacetic anilide. -p-anisidid. -3-ehloranilide. -5 -chlor- 2-toluidide. -o - loluidid. -cyclohexylamide. -octylamide. 2,4-dichlorobenz.oyl acetic acid amide.
Der Ringschluß des Hydrazons zum I-'arbsloff wird zweckmäßig in einem organischen Lösungsmittel wie Butanol. IsobuUnol. Pyridin. Dimethylsulfoxid. besonders vorteilhaft jedoch in Säuredialkylamiden wie Dimethylformamid. Dimethylacetamid. Hexamethylphosphorsäiiretriamid oder N - Methylpyrrolidon in Gegenwart einer basischen Verbindung wie Natrium- oder Kaliumacetat, -carbonai oder -hydroxid. Piperidin. Morpholin oder Triäthylamin bei Temperaturen zwischen etwa SO und etwa ISO C. gegebenenfalls unter Druck durchgeführt.The ring closure of the hydrazone to I-'arbsloff is conveniently in an organic solvent such as butanol. IsobuUnol. Pyridine. Dimethyl sulfoxide. particularly advantageous, however, in acid dialkylamides such as dimethylformamide. Dimethylacetamide. Hexamethylphosphoric acid triamide or N-methylpyrrolidone in the presence of a basic compound such as sodium or potassium acetate, carbonai or -hydroxide. Piperidine. Morpholine or triethylamine at temperatures between about SO and about ISO C. optionally carried out under pressure.
Falls das Hydrazon bereits in einem organischen Lösungsmittel der vorstehend genannten Art hergestellt wurde, kann es auch ohne vorherige Isolierung direkt in dem Reakiionsgemisch nach Neutralisation des sauren Kondensalionsmitlels durch Zusatz einer der genannten Basen cyclisiert werden. Der auskristallisierte Farbstoff kann in üblicher Weise abgetrennt werden.If the hydrazone has already been prepared in an organic solvent of the type mentioned above it can also be added directly to the reaction mixture after neutralization without prior isolation of the acidic condensation agent can be cyclized by adding one of the bases mentioned. The crystallized Dye can be separated off in the usual way.
Die als Ausgangsstoffe \erwendeten Benzoxanlhen- und Ben/othio:...: thendicarbonsäurehydrazide der Formel 11 sind aus der deutschen Patentschrift 1297 259. der LiSA.-Patentschrift 3 357 985. der britischen Patentschrift 1 245 478 und der deutschen Offenlegungsschrift 2 (X)S 491 bekannt.The Benzoxanlhen- and Ben / othio: ...: thendicarboxylic acid hydrazides used as starting materials Formula 11 are from the German patent specification 1297 259. the LiSA. patent specification 3 357 985. der British Patent 1,245,478 and German Offenlegungsschrift 2 (X) S 491 are known.
Die neuen erlindungsgemäß erhältlichen Farbstoffe eignen sich sehr gut zum Färben von synthetischen Materialien wie Acetylcellulosc. Polyamiden und insbesondere Polyäthylcnglykolterephthalat. Man erhält brillante gelbe bis rote Färbungen, die sich neben guter Lichtechtheit durch hervorragende Sublimiercchtheit auszeichnen. Wegen ihrer starken Fluoreszenz lassen sich die Verfahrensproduktc auch vorzüglich zur Herstellung von Tagesleuchtpigmenten verwenden. Sie können auch als Fluoreszenzfarbstoffc zum Färben von synthetischen Polymeren wie Polystyrol. Polymethacrylat und Polyvinylchlorid eingesetzt werden. Sie ergeben in diesen Materialien gelbe bis rote Farbtöne, die intensiv gelbgrün bisThe new dyes available according to the invention are very suitable for dyeing synthetic ones Materials such as acetyl cellulose c. Polyamides and in particular Polyäthylcnglykolterephthalat. Man Obtains brilliant yellow to red colorations which, in addition to good lightfastness, are distinguished by excellent sublimation fastness distinguish. Because of their strong fluorescence, the process products can also Excellent to use for the production of daytime luminescent pigments. They can also be used as fluorescent dyes for coloring synthetic polymers such as polystyrene. Polymethacrylate and polyvinyl chloride are used will. In these materials, they result in yellow to red shades, the intensely yellow-green to
509 620/233509 620/233
orange fluoreszieren und sich durch hohe Hitzebeständigkeit und Lichtechtheit auszeichnen.fluoresce orange and are characterized by high heat resistance and lightfastness.
Ein weiteres Anwendungsgebiet ist das Farben von synthetischen, faserbildenden Polymeren wie Polyäthylenglykolterephthalat in der Masse.Another area of application is the coloring of synthetic, fiber-forming polymers such as Polyethylene glycol terephthalate in bulk.
Außerdem ist ein großer Teil der Verfahrensprodukte auch sehr gut zum Fürben von synthetischen Materialien aus organischen Lösemitteln wie Perchloräthylen geeignet.In addition, a large part of the process products is also very good for tanning synthetic products Materials made from organic solvents such as perchlorethylene are suitable.
IOIO
a) 20.0 g Benzothioxanthen - 3.4 - dicarbonsäurehydrazid und 0.5 g Toluolsulfonsäure werden in 120 g Acetessigsäureäthylestcr 1 Stunde unter Durchleiten eines schwachen Stickstoffstromes bei 135 bis 140 C gerührt. Nach dem lirkalten verdünnt man die Reaktionsmischung mit 140 ml Methanol, saugt das gebildete orangefarbene Hydrazon ab. wäscht mil Methanol und Wasser und trocknet.a) 20.0 g of benzothioxanthene-3.4-dicarboxylic acid hydrazide and 0.5 g of toluenesulfonic acid are dissolved in 120 g of ethyl acetoacetate for 1 hour while being passed through a gentle stream of nitrogen at 135 to 140 ° C. After the cold one dilutes the Reaction mixture with 140 ml of methanol, sucks off the orange hydrazone formed. washes mil Methanol and water and dries.
b) Line Mischung von 11.0 g des gemäß al erhaltenen Hydrazone. 110 ml Dimethylformamid und 0,11g wasserfreiem Kaliumacetat wird 30 Minuten zum Sieden erhitzt. Nach dem Lrkalten wird das auskristalüsierte rote Farbstoffisomerengemisch der Formelb) Line mixture of 11.0 g of the hydrazone obtained according to al. 110 ml of dimethylformamide and 0.11g of anhydrous potassium acetate is used for 30 minutes heated to boiling. After cooling, the red dye isomer mixture that has crystallized out becomes the formula
N-NN-N
C- CH,C- CH,
COOCH5 COOCH 5
Cw1UOOC-C-C-CH,Cw 1 UOOC-CC-CH,
j! Nj! N
L- οL- ο
serfreiem Kaliumacetat gemäß Beispiel 1 b) zui orangeroten Isomerengemisch der Formelser-free potassium acetate according to Example 1 b) zui orange-red mixture of isomers of the formula
N-NN-N
I IlI Il
C-CH,C-CH,
CH3O-CH 3 O-
frfr
COCH,COCH,
CH3OC -C— C-CH,CH 3 OC -C— C-CH,
i!i!
CH3OCH 3 O
eyclisieri. An Stelle \on Kaliuniacei;it kann die Cycli sierung auch in Gegenwart der gleichen Gewichts menge Piperidin oder Morpholin erfolgen. Diesel Farbstoff färbt Polystyrol und Polymethacrylat ir leuchtend orangegelben intensiv fluoreszierender 1 arbtönen. Die Färbungen besitzen eine hohe thermische Stabilität und sehr gute 1 ichlechtheil.eyclisieri. Instead of \ on Kaliuniacei; it the Cycli can also be carried out in the presence of the same amount by weight of piperidine or morpholine. diesel Dye colors polystyrene and polymethacrylate ir bright orange-yellow, intensely fluorescent 1 shades. The dyeings have a high thermal value Stability and very good health.
al ').i s Benzothioxanthen - 3.4-dicarhonsäurehydrazid. IMI 1; Aceiondic.irbonsauredimethylester und 0.05 g Toluolsulfonsä'ure werden in 130 ml Chlorbenzol S Stunden unter Rückfluß am Sieden gehalten. Das entstandene orangefarbene Hydrazon wird inal ') .i s Benzothioxanthene - 3,4-dicarhonic acid hydrazide. IMI 1; Aceiondic.irbonsauredimethylester and 0.05 g of toluenesulfonic acid in 130 ml of chlorobenzene are kept at the boil for 5 hours under reflux. The resulting orange hydrazone is in
bekannter Weise isoliert.known way isolated.
h| 4.2 g des gemäß Beispiel 3al erhaltenen Hvdra/ons werden in 46 ml Dimethylformamid nach Zugabe \on 0.09 g wasserfreiem Kaliumacelat !5MiIiUtCIi auf 145 bis 150 C erhitzt. Nach dem Frkahen wird mit Methanol verdünnt und die rotorange l-arhsiolTinischimg der 1-ormel Oh | 4.2 g of the Hvdra / on obtained according to Example 3al are in 46 ml of dimethylformamide after adding 0.09 g of anhydrous potassium acetate ! 5MiIiUtCIi heated to 145 to 150 C. After this Frkahen is diluted with methanol and the red-orange l-arhsiolTinischimg der 1-ormel O
ibgesaugt. mit Methanol und Wasser gewaschen und retrocknet. [Die aus Dimethylformamid umkristalliierte Verbindung ersiab folgende Analvsenwerte:ibgesuckt. washed with methanol and water and redried. [The recrystallized from dimethylformamide Connection ersiab the following analysis values:
"N-"N-
Berechnet . . . C 72.2. H 3.7. N 7.3. S 8.4:
gefunden . . C 71.9. H 3.9. N 7.7. S 8.3.Calculated . . . C 72.2. H 3.7. N 7.3. S 8.4:
found . . C 71.9. H 3.9. N 7.7. S 8.3.
5555
6060
Polystyrol- und Polymcthacrylatmaterialien lasen sich mit diesem Farbstoff in stark fluoreszierenden irangeroten Farbtönen hoher Lichtechtheit und sehr uter Temperaturbeständigkeit anfärben.Polystyrene and polymethyl acrylate materials read strongly fluorescent with this dye Dye orange-red shades of high lightfastness and very low temperature resistance.
a) 20.0 g lO-Meihoxybenzoxanthen^M-dicarboniurehydrazid. 150 g Acetylaceton und 0.2 g Toluolalfonsäure werden gemäß Beispiel la) zum ent- ^rechenden Hydrazon kondensiert.a) 20.0 g 10-Meihoxybenzoxanthene ^ M-dicarboniurehydrazid. 150 g of acetylacetone and 0.2 g of toluene alfonic acid are used in accordance with Example la) to ^ reckoning hydrazone condensed.
b) 23,0 g dieses Hydrazons werden in 200 ml I-Methylpyrrolidcn in Gegenwart von 0.23 g was-N
Cb) 23.0 g of this hydrazone are dissolved in 200 ml of I-methylpyrrolidene in the presence of 0.23 g of was-N
C.
ClI,CO(XH1 ClI, CO (XH 1
C
COOCH3 C.
COOCH 3
CH3OOC-C C-CH2COOCH3 CH 3 OOC-C C -C -CH 2 COOCH 3
in bekannter Weise isoliert. Auf Polvestermaterialienisolated in a known manner. On Pole Eve materials
erhält man mit diesem Farbstoff sublimierechle klare orange Fürbungen.With this dye sublimierechle, clear orange tints are obtained.
a) Ein Gemisch von 16.6 g 6-Methoxybenzoxanthen-3.4-dicarbonsäurchydrazid, 96 g Stearoylessigsäurciithylester und 0,16 g Toluolsulfonsäure wird 10 Stunden bei I75"C gerührt. Bei Raumtemperatur verdünnt man die qrangegelbe Lösung mit 100 ml Bulylacetal und läßt mehrere Stunden rühren. Das dabei auskrislallisicrende gelbe Hydrazon wird in bekannter Weise isoliert.a) A mixture of 16.6 g of 6-methoxybenzoxanthene-3,4-dicarboxylic acid hydrazide, 96 g of stearoyl acetic acid dithyl ester and 0.16 g of toluenesulphonic acid Stirred for 10 hours at 175 ° C. At room temperature, the quran-yellow solution is diluted with 100 ml Bulyl acetal and let stir for several hours. The thereby auskrislallisicrende yellow hydrazone is in known way isolated.
b) 15,0 g des gemäß a) erhaltenen Hydra/ons werden in 75 ml Dimethylformamid in Gegenwart von 0.15 g wasserfreiem Kaliumacetal in 15 Minuten bei 145 bis 150" C /um Farbstoffisomerengcmisch der Formelb) 15.0 g of the hydra / on obtained according to a) are in 75 ml of dimethylformamide in the presence of 0.15 g of anhydrous potassium acetal in 15 minutes at 145 to 150 "C / um mixture of dye isomers of the formula
C2H5OOC-C-C-(CH2UCH3 C 2 H 5 OOC-CC- (CH 2 UCH 3
OCH3 OCH 3
kondensiert. Das in Aromalenlösungsmitteln sehr gut lösliche orangegelbe Produkt färbt Hart-PVC in kräftig fluoreszierenden orangegelben Farbtöner hoher Lichtechtheit und sehr guter thermischer Stabilität. condensed. The orange-yellow product, which is very soluble in flavoring solvents, stains rigid PVC in strong fluorescent orange-yellow color, high lightfastness and very good thermal stability.
In der nachfolgenden Tabelle sind weitere Färbstoffe aufgeführt, die nach den in den obigen Beispielen beschriebenen Arbeitsweisen erhalten werdenFurther dyes are shown in the table below listed, which are obtained according to the procedures described in the above examples
C—(CH2)lftCH,C— (CH 2 ) lft CH,
COOC2H5 COOC 2 H 5
OCH3 OCH 3
C-R1 + Isom.CR 1 + isom.
Tabelle siehe Spalte 13 bis 16Table see columns 13 to 16
CH,CH,
COOC1H,COOC 1 H,
Farbton (PoIyM) rol|Color (PoIyM) rol |
orangegelborange yellow
orangeorange
orangerotOrange red
orangeorange
orangerotOrange red
rotorangeRed orange
orangegelborange yellow
orangeorange
orange orangegelb orange orange orangerot orange orangerot orangegelb orange orargerot orange orangerotorange orange-yellow orange orange orange-red orange orange-red orange-yellow orange orange red orange orange red
orangeorange
orangerotOrange red
orangerotOrange red
blaustichigrotbluish red
blaustichigroibluish gray
rotRed
rotviolettred-violet
Fortsetzungcontinuation
CH3 CH3 CH3 CH3 CH3 CH 3 CH 3 CH 3 CH 3 CH 3
CH3 CH 3
CH3 CH 3
CH3 CH 3
CH3 CH 3
<CH2)ltlCH3 <CH 2 ) ltl CH 3
CH2COOCH3 CH 2 COOCH 3
COOC2H5 COOC 2 H 5
COOC2H5 j -CH3 COOC 2 H 5 j -CH 3
; — ( x ; - ( x
R.R.
ί -CH3 ί -CH 3
-COOC2H5 -COOC2H5 -COOC 2 H 5 -COOC 2 H 5
— COOCH3 - COOCH 3
— COOC4H9 - COOC 4 H 9
— COOCH2CH(CH2)3CH3 - COOCH 2 CH (CH 2 ) 3 CH 3
C2H5 C 2 H 5
-COO(CH2)UCH3 -COO(CH2J11CH3 -COO(CH2J16CH3 -COO(CH2J16CH3 -COOC2H5 -COOCH3 -COO (CH 2 ) U CH 3 -COO (CH 2 J 11 CH 3 -COO (CH 2 J 16 CH 3 -COO (CH 2 J 16 CH 3 -COOC 2 H 5 -COOCH 3
— COOC2H5 -COOC2H5 - COOC 2 H 5 -COOC 2 H 5
—c on η —/ y —C on η - / y
— COCH3 - COCH 3
— COCH3 - COCH 3
— COOC2H5 - COOC 2 H 5
-CONH2 -CONH 2
-COOC2H5 -COOC 2 H 5
-COOC2H5 -COOC 2 H 5
-COO(CH2J17CH3 -COO (CH 2 J 17 CH 3
-COO(CH2J17CH3 -COO (CH 2 J 17 CH 3
-COO(CH2J17CH3 -COO (CH 2 J 17 CH 3
H
H
H
H
HH
H
H
H
H
— OCH3
H- OCH 3
H
— OCH3
H- OCH 3
H
— OCH3
H- OCH 3
H
— OCH3 - OCH 3
H
HH
H
H H H H HH H H H H
H H HH H H
H H H HH H H H
H HH H
iH i H
ι I H ι IH
H H H H H HH H H H H H
H H H H H H H HH H H H H H H H
H H H HH H H H
N) LM OON) LM OO
LM LM OLM LM O
Claims (10)
COOC2H5 Γ
COOC 2 H 5
C-C-CH1COOCH,COOCH 3
CC-CH 1 COOCH,
COO(CH2I1-CH, J
COO (CH 2 I 1 -CH,
[
C-C- CH,COO (CH 2 I 1 -CH,
[
CC- CH,
N'N
N '
i['
i
Priority Applications (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2238330A DE2238330C3 (en) | 1972-08-04 | 1972-08-04 | Benzoxanthene and benzothioxanthene dyes and processes for their preparation |
| CH1116373A CH578036A5 (en) | 1972-08-04 | 1973-07-31 | |
| US00384785A US3853884A (en) | 1972-08-04 | 1973-08-02 | Benzoxanthene and benzothioxanthene dyestuffs |
| GB3673673A GB1435955A (en) | 1972-08-04 | 1973-08-02 | Benzoxanthene and benzothioxanthene dyestuffs and process for preparing them |
| AR249417A AR197518A1 (en) | 1972-08-04 | 1973-08-02 | BENZOXANTHENES AND BENZOTHIOZANTHENES DYES AND PROCEDURE FOR THEIR PREPARATION |
| JP48086438A JPS5927780B2 (en) | 1972-08-04 | 1973-08-02 | Benzoxanthene and benzothioxanthene dyes and their production method |
| IT27459/73A IT998318B (en) | 1972-08-04 | 1973-08-02 | DYES OF BENZOXANTHENE AND BENZOTHIOXANTHENE AND PROCEDURE FOR THEIR PREPARATION |
| BR5941/73A BR7305941D0 (en) | 1972-08-04 | 1973-08-03 | PROCESS FOR THE PREPARATION OF BENZONANTENE AND BENZOTIOXANTHEN DYES |
| CA178,048A CA1021341A (en) | 1972-08-04 | 1973-08-03 | Benzoxanthene and benzothioxanthene dyestuffs and process for preparing them |
| FR7328454A FR2194754B1 (en) | 1972-08-04 | 1973-08-03 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2238330A DE2238330C3 (en) | 1972-08-04 | 1972-08-04 | Benzoxanthene and benzothioxanthene dyes and processes for their preparation |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DE2238330A1 DE2238330A1 (en) | 1974-03-21 |
| DE2238330B2 DE2238330B2 (en) | 1974-09-05 |
| DE2238330C3 true DE2238330C3 (en) | 1975-05-15 |
Family
ID=5852613
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE2238330A Expired DE2238330C3 (en) | 1972-08-04 | 1972-08-04 | Benzoxanthene and benzothioxanthene dyes and processes for their preparation |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US3853884A (en) |
| JP (1) | JPS5927780B2 (en) |
| AR (1) | AR197518A1 (en) |
| BR (1) | BR7305941D0 (en) |
| CA (1) | CA1021341A (en) |
| CH (1) | CH578036A5 (en) |
| DE (1) | DE2238330C3 (en) |
| FR (1) | FR2194754B1 (en) |
| GB (1) | GB1435955A (en) |
| IT (1) | IT998318B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR870001253B1 (en) * | 1985-01-10 | 1987-06-29 | 진웅기업 주식회사 | Method and device for waterproofing and fitting of waterproofing tape of seam tapes |
| DE4202911A1 (en) * | 1992-02-01 | 1993-08-05 | Cassella Ag | DYE MIXTURES FOR DYING TEXTILE HYDROPHOBIC FIBER MATERIALS |
| GB9404020D0 (en) * | 1994-03-02 | 1994-04-20 | Zeneca Ltd | Process |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1293364B (en) * | 1965-02-24 | 1969-04-24 | Hoechst Ag | Process for the production of dyes |
-
1972
- 1972-08-04 DE DE2238330A patent/DE2238330C3/en not_active Expired
-
1973
- 1973-07-31 CH CH1116373A patent/CH578036A5/xx not_active IP Right Cessation
- 1973-08-02 JP JP48086438A patent/JPS5927780B2/en not_active Expired
- 1973-08-02 US US00384785A patent/US3853884A/en not_active Expired - Lifetime
- 1973-08-02 GB GB3673673A patent/GB1435955A/en not_active Expired
- 1973-08-02 AR AR249417A patent/AR197518A1/en active
- 1973-08-02 IT IT27459/73A patent/IT998318B/en active
- 1973-08-03 CA CA178,048A patent/CA1021341A/en not_active Expired
- 1973-08-03 BR BR5941/73A patent/BR7305941D0/en unknown
- 1973-08-03 FR FR7328454A patent/FR2194754B1/fr not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE2238330B2 (en) | 1974-09-05 |
| JPS5927780B2 (en) | 1984-07-07 |
| GB1435955A (en) | 1976-05-19 |
| AR197518A1 (en) | 1974-04-15 |
| FR2194754A1 (en) | 1974-03-01 |
| CH578036A5 (en) | 1976-07-30 |
| CA1021341A (en) | 1977-11-22 |
| DE2238330A1 (en) | 1974-03-21 |
| BR7305941D0 (en) | 1974-05-16 |
| JPS4959832A (en) | 1974-06-11 |
| IT998318B (en) | 1976-01-20 |
| FR2194754B1 (en) | 1977-02-25 |
| US3853884A (en) | 1974-12-10 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C3 | Grant after two publication steps (3rd publication) | ||
| E77 | Valid patent as to the heymanns-index 1977 | ||
| 8339 | Ceased/non-payment of the annual fee |